KR102592106B1 - Modified resin and golf balls for molded bodies - Google Patents

Modified resin and golf balls for molded bodies Download PDF

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KR102592106B1
KR102592106B1 KR1020207026544A KR20207026544A KR102592106B1 KR 102592106 B1 KR102592106 B1 KR 102592106B1 KR 1020207026544 A KR1020207026544 A KR 1020207026544A KR 20207026544 A KR20207026544 A KR 20207026544A KR 102592106 B1 KR102592106 B1 KR 102592106B1
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ethylene
modified resin
guanidine
acid copolymer
unsaturated carboxylic
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KR20200121340A (en
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다카히로 시미즈
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미츠이·다우 폴리케미칼 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
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    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/0023—Covers
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    • A—HUMAN NECESSITIES
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    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • A—HUMAN NECESSITIES
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    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
    • A63B37/0039—Intermediate layers, e.g. inner cover, outer core, mantle characterised by the material
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/005—Cores
    • A63B37/0051—Materials other than polybutadienes; Constructional details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof

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Abstract

본 발명은, 에틸렌·불포화 카르본산 공중합체를 구아니딘 탄산염으로 변성한 성형체용 변성 수지로서, 에틸렌·불포화 카르본산 공중합체 멜트 플로우 레이트가 20(g/10분) 이상 600(g/10분) 이하인 성형체용 변성 수지이다.The present invention is a modified resin for molded products obtained by modifying an ethylene/unsaturated carboxylic acid copolymer with guanidine carbonate, wherein the ethylene/unsaturated carboxylic acid copolymer has a melt flow rate of 20 (g/10 min) or more and 600 (g/10 min) or less. It is a modified resin for molded products.

Description

성형체용 변성 수지 및 골프 볼Modified resin and golf balls for molded bodies

본 발명은, 성형체용 변성 수지 및 골프 볼에 관한 것이다.The present invention relates to modified resins for molded articles and golf balls.

최근, 에틸렌 단독 중합체, 에틸렌과 다른 올레핀과의 공중합체, 에틸렌과 불포화 카르본산과의 공중합체 등의 폴리올레핀계 수지는 다양한 분야에서 이용되고 있다. 예를 들면, 폴리올레핀계 수지에 수산화 마그네슘이나 수산화 알루미늄 등을 배합한 것은 난연성이 우수한 점에서, 전선의 피복 재료 또는 전기 전자기기의 부재에 이용되고 있다. 또한, 용도에 따라서는, 산 변성 또는 염기성 화합물을 첨가하는 등 하여 폴리올레핀계 수지의 개질이 널리 행해지고 있다.Recently, polyolefin resins such as ethylene homopolymers, copolymers of ethylene with other olefins, and copolymers of ethylene with unsaturated carboxylic acids are used in various fields. For example, polyolefin resin mixed with magnesium hydroxide or aluminum hydroxide is excellent in flame retardancy and is used as a covering material for electric wires or components of electrical and electronic devices. Additionally, depending on the use, modification of polyolefin resins is widely performed, such as by acid modification or addition of basic compounds.

염기성 화합물을 첨가한 수지로서, 예를 들면, 특허 문헌 1에는, 산 변성 폴리올레핀의 구아니딘 화합물의 염을 포함하는 난연성 수지 조성물이 개시되어 있다. 이 난연성 수지 조성물에 의하면, 난연성에 더해, 기계 특성에도 우수한 것이 기재되어 있다.As a resin to which a basic compound has been added, for example, Patent Document 1 discloses a flame-retardant resin composition containing a salt of a guanidine compound of acid-modified polyolefin. According to this flame retardant resin composition, it is described that in addition to flame retardancy, it is also excellent in mechanical properties.

또한, 특허 문헌 2에는, 에틸렌-비닐에스테르계 공중합체 비누화물, 및 염기성 아민 화합물을 함유하는 에틸렌-비닐에스테르계 공중합체 비누화물 조성물이 개시되어 있다. 이 조성물을 함유시킨 재료는 폴리에스테르계 수지와의 접착성이 향상되기 때문에 다층 구조체에 유용한 것이 기재되어 있다.Additionally, Patent Document 2 discloses a saponified ethylene-vinyl ester copolymer and a saponified ethylene-vinyl ester copolymer composition containing a basic amine compound. It is described that materials containing this composition are useful for multilayer structures because their adhesion to polyester resins is improved.

게다가 또한, 특허 문헌 3에는, 폴리올레핀에 구아니딘 인산염을 첨가한 폴리올레핀계 수지 조성물이 개시되어 있다. 이 폴리올레핀계 수지 조성물에 의하면, 연소 시의 부식성 가스의 발생을 억제하면서 우수한 기계 특성을 실현할 수 있는 것이 기재되어 있다.Furthermore, Patent Document 3 discloses a polyolefin-based resin composition obtained by adding guanidine phosphate to polyolefin. According to this polyolefin-based resin composition, it is described that excellent mechanical properties can be realized while suppressing the generation of corrosive gas during combustion.

한편, 에틸렌과 (메타)아크릴산과의 공중합체를 금속 이온으로 중화(中和)한 아이오노머는, 높은 경도와 반발 탄성을 가지는 점에서, 골프 볼 등을 구성하는 탄성 재료층에 이용되고 있다(특허 문헌 4 참조). 골프 볼에서는, 투피스 볼, 스리피스 볼, 또는 포 피스 볼과 같은 중심부의 코어를 복수의 탄성 재료층으로 피복하여, 최외층 커버를 마련한 다층 골프 볼이 주류이다.On the other hand, ionomer, which is a copolymer of ethylene and (meth)acrylic acid neutralized with metal ions, has high hardness and rebound elasticity, and is used in the elastic material layer constituting golf balls etc. ( (see patent document 4). Among golf balls, multilayer golf balls, such as two-piece balls, three-piece balls, or four-piece balls, in which a central core is covered with a plurality of elastic material layers and an outermost layer cover is provided, are the most common.

다층 골프 볼에 있어서, 코어, 커버층, 코어와 커버층과의 사이의 층(중간층)의 재질은, 볼의 반발력, 초속도, 비거리, 스핀 성능, 및 타구감에 영향을 준다. 일반적으로는, 코어에는 부타디엔 고무, 중간층에는 아이오노머계 수지, 커버층에는 우레탄 수지나 아이오노머 수지가 사용되고 있다. 각각의 층에 이용하는 재료를 적절히 선택하고, 조합함으로써, 각각의 골프 볼 브랜드에 특징적인, 반발력, 초속도, 비거리, 스핀 성능, 및 타구감이 조절되고 있다.In a multilayer golf ball, the materials of the core, the cover layer, and the layer between the core and the cover layer (middle layer) affect the ball's repulsion force, initial speed, distance, spin performance, and feel. Generally, butadiene rubber is used for the core, ionomer resin is used for the middle layer, and urethane resin or ionomer resin is used for the cover layer. By appropriately selecting and combining the materials used in each layer, the repulsion force, initial speed, distance, spin performance, and shot feel characteristic of each golf ball brand are adjusted.

일본 공개특허 특개2007-321024호 공보Japanese Patent Laid-Open No. 2007-321024 일본 공개특허 특개2012-107197호 공보Japanese Patent Laid-Open No. 2012-107197 일본 공개특허 특개평6-25476호 공보Japanese Patent Laid-open Publication No. 6-25476 일본 공개특허 특개평11-299933호 공보Japanese Patent Laid-open Publication No. 11-299933

그러나, 상기 특허 문헌에 기재된 기계 특성이 우수한 수지를 골프 볼 등의 볼 재료로서 사용하기 위해서는, 반발 탄성률, 경도 및 굽힘 강성률에 있어서, 더욱 개량의 여지가 있다.However, in order to use the resin with excellent mechanical properties described in the above patent document as a ball material such as a golf ball, there is room for further improvement in terms of rebound modulus, hardness, and bending rigidity.

본 발명은 상기 사정을 고려하여 이루어진 것이며, 반발 탄성률, 경도 및 굽힘 강성률이 우수한 성형체용 변성 수지 및 그 성형체용 변성 수지를 이용한 골프 볼을 제공하는 것을 목적으로 한다.The present invention was made in consideration of the above circumstances, and its purpose is to provide a modified resin for a molded body with excellent rebound modulus, hardness, and bending rigidity, and a golf ball using the modified resin for a molded body.

본 발명자들은, 특정 범위의 멜트 플로우 레이트를 가지는 에틸렌·불포화 카르본산 공중합체를 구아니딘 유도체 및 그 염으로부터 선택되는 적어도 1종의 구아니딘 화합물로 변성함으로써 얻어진 변성 수지가, 반발 탄성률, 경도 및 굽힘 강성률이 우수한 것을 발견하여, 본원 발명에 이르렀다.The present inventors have found that a modified resin obtained by modifying an ethylene-unsaturated carboxylic acid copolymer having a melt flow rate in a specific range with at least one guanidine compound selected from guanidine derivatives and salts thereof has a rebound modulus, hardness, and bending rigidity. An excellent discovery was made, leading to the present invention.

즉, 본 발명의 성형체용 변성 수지는,That is, the modified resin for molded articles of the present invention is,

에틸렌·불포화 카르본산 공중합체를 구아니딘 유도체 및 그 염으로부터 선택되는 적어도 1종의 구아니딘 화합물로 변성한 성형체용 변성 수지로서,A modified resin for molded articles obtained by modifying an ethylene-unsaturated carboxylic acid copolymer with at least one guanidine compound selected from guanidine derivatives and salts thereof,

에틸렌·불포화 카르본산 공중합체의 멜트 플로우 레이트가, 20(g/10분) 이상 600(g/10분) 이하이다.The melt flow rate of the ethylene/unsaturated carboxylic acid copolymer is 20 (g/10 min) or more and 600 (g/10 min) or less.

여기서, 멜트 플로우 레이트(이하, MFR이라고 함)는, 온도 190℃, 재하 하중 2160g에서, JIS K7210(1999)에 따라 측정한 값이다.Here, the melt flow rate (hereinafter referred to as MFR) is a value measured according to JIS K7210 (1999) at a temperature of 190°C and a load of 2160 g.

에틸렌·불포화 카르본산 공중합체는, 에틸렌·(메타)아크릴산 공중합체인 것이 바람직하다.The ethylene/unsaturated carboxylic acid copolymer is preferably an ethylene/(meth)acrylic acid copolymer.

에틸렌·불포화 카르본산 공중합체 중의 불포화 카르본산에 유래하는 구성 단위의 함유량은, 에틸렌·불포화 카르본산 공중합체의 구성 단위의 합계에 대하여, 10질량% 이상 30질량% 이하인 것이 바람직하다.The content of the structural unit derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid copolymer is preferably 10% by mass or more and 30% by mass or less relative to the total of the structural units of the ethylene/unsaturated carboxylic acid copolymer.

성형체용 변성 수지는, 변성 수지 중의 에틸렌·불포화 카르본산 공중합체에 포함되는 불포화 카르본산 유래의 카르복실기의 총 몰수 (A)에 대한 변성 수지 중의 구아니딘 화합물의 구아니디노기 또는 구아니디늄 이온의 총 몰수 (B)의 비(B/A)가 0.05 이상 0.8 이하로 변성하는 것이 바람직하다.The modified resin for molded products is the total number of guanidino groups or guanidinium ions of the guanidine compound in the modified resin relative to the total number of moles (A) of carboxyl groups derived from unsaturated carboxylic acid contained in the ethylene/unsaturated carboxylic acid copolymer in the modified resin. It is preferable that the ratio (B/A) of the number of moles (B) is modified to be 0.05 or more and 0.8 or less.

구아니딘 유도체의 염은 구아니딘 탄산염인 것이 바람직하다.The salt of the guanidine derivative is preferably guanidine carbonate.

성형체용 변성 수지는, 에틸렌·불포화 카르본산 공중합체와, 구아니딘 유도체 및 그 염으로부터 선택되는 적어도 1종의 구아니딘 화합물을 용융 혼련하여 얻어진 것인 것이 바람직하다.The modified resin for molded articles is preferably obtained by melt-kneading an ethylene-unsaturated carboxylic acid copolymer and at least one guanidine compound selected from guanidine derivatives and salts thereof.

본 발명의 골프 볼은, 본 발명의 성형체용 변성 수지를 포함한다.The golf ball of the present invention contains the modified resin for molded articles of the present invention.

본 발명에 의하면, 반발 탄성률, 경도 및 굽힘 강성률이 우수한 성형체용 변성 수지 및 골프 볼을 얻을 수 있다.According to the present invention, a modified resin for a molded body and a golf ball with excellent rebound modulus, hardness, and bending rigidity can be obtained.

이하, 본 발명의 성형체용 변성 수지 및 골프 볼에 대하여 설명한다.Hereinafter, the modified resin for molded articles and the golf ball of the present invention will be described.

[성형체용 변성 수지][Modified resin for molded body]

본 발명의 성형체용 변성 수지는, 에틸렌·불포화 카르본산 공중합체를 구아니딘 유도체 및 그 염으로부터 선택되는 적어도 1종의 구아니딘 화합물로 변성한 성형체용 변성 수지로서, 에틸렌·불포화 카르본산 공중합체의 MFR이 20(g/10분) 이상 600(g/10분) 이하인 성형체용 변성 수지이다.The modified resin for molded articles of the present invention is a modified resin for molded articles obtained by modifying an ethylene/unsaturated carboxylic acid copolymer with at least one guanidine compound selected from guanidine derivatives and salts thereof, and the MFR of the ethylene/unsaturated carboxylic acid copolymer is It is a modified resin for molded products with a weight of 20 (g/10 min) or more and 600 (g/10 min) or less.

본 발명의 실시 형태와 관련된 에틸렌·불포화 카르본산 공중합체의 MFR은, 반발 탄성률, 경도 및 굽힘 강성률 향상의 관점에서, 보다 바람직하게는, 20(g/10분) 이상 500(g/10분) 이하이며, 더 바람직하게는 20(g/10분) 이상 300(g/10분) 이하이다.The MFR of the ethylene-unsaturated carboxylic acid copolymer according to the embodiment of the present invention is more preferably 20 (g/10 min) or more than 500 (g/10 min) from the viewpoint of improving the rebound modulus, hardness, and bending rigidity. or less, and more preferably 20 (g/10 min) or more and 300 (g/10 min) or less.

수평균 분자량으로서는, 폴리스티렌 환산으로 10000 정도~30000 정도가 바람직하다.The number average molecular weight is preferably about 10,000 to about 30,000 in terms of polystyrene.

반발 탄성률, 경도 및 굽힘 강성률 향상의 관점에서 에틸렌·불포화 카르본산 공중합체에 포함되는 불포화 카르본산 유래의 카르복실기의 총 몰수에 대한 구아니딘 화합물 중의 구아니디노기 또는 구아니디늄 이온의 몰비가 0.05 이상 0.8 이하로 변성하는 것이 바람직하지만, 보다 바람직하게는 0.05 이상 0.7 이하이며, 더 바람직하게는 0.05 이상 0.6 이하이다.From the viewpoint of improving the rebound modulus, hardness, and bending rigidity, the molar ratio of the guanidino group or guanidinium ion in the guanidine compound to the total number of moles of carboxyl groups derived from unsaturated carboxylic acid contained in the ethylene-unsaturated carboxylic acid copolymer is 0.05 or more and 0.8. It is preferable to modify it to 0.05 to 0.7, more preferably 0.05 to 0.6.

(에틸렌·불포화 카르본산 공중합체)(Ethylene/unsaturated carboxylic acid copolymer)

본 발명의 실시 형태와 관련된 성형체용 변성 조성물에 있어서의 에틸렌·불포화 카르본산 공중합체는, 에틸렌 및 불포화 카르본산만으로 이루어지는 공중합체에 한정되지 않고, 임의로 그 밖의 공중합 성분이 공중합된 다원 공중합체여도 된다.The ethylene-unsaturated carboxylic acid copolymer in the modified composition for molded products according to the embodiment of the present invention is not limited to a copolymer consisting of only ethylene and unsaturated carboxylic acid, and may optionally be a multi-component copolymer in which other copolymerization components are copolymerized. .

에틸렌·불포화 카르본산 공중합체의 불포화 카르본산으로서는, 아크릴산, 메타크릴산, 에타크릴산, 푸마르산, 크로톤산, 말레산, 이타콘산, 말레산 모노메틸, 말레산 모노에틸, 무수 말레산, 무수 이타콘산 등의 탄소수 4~8의 불포화 카르본산 등을 예시할 수 있고, 특히 아크릴산 혹은 메타크릴산이 바람직하다. 불포화 카르본산은 1종이어도, 2종 이상이어도 된다.Examples of unsaturated carboxylic acids in the ethylene/unsaturated carboxylic acid copolymer include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, crotonic acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and itaconic anhydride. Examples include unsaturated carboxylic acids having 4 to 8 carbon atoms, such as conic acid, and acrylic acid or methacrylic acid is particularly preferable. The number of unsaturated carboxylic acids may be one, or two or more types may be used.

임의의 다른 공중합 성분으로서는, 예를 들면, 아크릴산 메틸, 아크릴산 에틸, 아크릴산 이소부틸, 아크릴산 n부틸, 아크릴산 이소옥틸, 메타크릴산 메틸, 메타크릴산 에틸, 메타크릴산 이소부틸, 메타크릴산 n부틸, 말레산 디메틸, 말레산 디에틸 등의 불포화 카르본산 에스테르; 프로필렌, 부텐, 1,3-부타디엔, 펜텐, 1,3-펜타디엔, 1-헥센 등의 불포화 탄화수소; 아세트산 비닐, 프로피온산 비닐 등의 비닐에스테르; 비닐 황산이나 비닐 질산 등의 산화물; 염화 비닐, 불화 비닐 등의 할로겐화물; 비닐기 함유 1, 2급 아민 화합물; 일산화 탄소; 이산화 유황 등을 예시할 수 있다.Optional other copolymerization components include, for example, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, and n-butyl methacrylate. , unsaturated carboxylic acid esters such as dimethyl maleate and diethyl maleate; Unsaturated hydrocarbons such as propylene, butene, 1,3-butadiene, pentene, 1,3-pentadiene, and 1-hexene; Vinyl esters such as vinyl acetate and vinyl propionate; Oxides such as vinyl sulfate and vinyl nitric acid; Halides such as vinyl chloride and vinyl fluoride; vinyl group-containing primary and secondary amine compounds; carbon monoxide; Examples include sulfur dioxide and the like.

에틸렌·불포화 카르본산계 공중합체는, 블록 공중합체, 랜덤 공중합체, 그래프트 공중합체 중 어느 것이어도 된다. 공업적으로 입수 가능한 관점에서, 2원 랜덤 공중합체, 3원 랜덤 공중합체, 또는, 2원 랜덤 공중합체의 그래프트 공중합체 혹은 3원 랜덤 공중합체의 그래프트 공중합체를 이용하는 것이 바람직하다. 보다 바람직하게는 2원 랜덤 공중합체 또는 3원 랜덤 공중합체이다.The ethylene-unsaturated carboxylic acid-based copolymer may be any of block copolymers, random copolymers, and graft copolymers. From the viewpoint of industrial availability, it is preferable to use a binary random copolymer, a ternary random copolymer, or a graft copolymer of a binary random copolymer or a graft copolymer of a ternary random copolymer. More preferably, it is a binary random copolymer or a ternary random copolymer.

-불포화 카르본산에 유래하는 구성 단위의 함유량--Content of structural units derived from unsaturated carboxylic acid-

에틸렌·불포화 카르본산 공중합체 중의 불포화 카르본산에 유래하는 구성 단위의 함유량은, 에틸렌·불포화 카르본산 공중합체의 구성 단위의 합계에 대하여, 10질량% 이상 30질량% 이하가 바람직하다. 바람직하게는, 12질량% 이상 26질량% 이하이며, 더 바람직하게는, 14질량% 이상 22질량% 이하이다.The content of the structural unit derived from the unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid copolymer is preferably 10% by mass or more and 30% by mass or less relative to the total of the structural units of the ethylene/unsaturated carboxylic acid copolymer. Preferably, it is 12 mass% or more and 26 mass% or less, and more preferably, it is 14 mass% or more and 22 mass% or less.

상기 서술의 임의 공중합 성분은, 일반적으로는 15몰% 이하, 바람직하게는 10몰% 이하의 비율로 공중합되어 있어도 된다. 이와 같은 에틸렌·불포화 카르본산 공중합체는, 특별히 제한은 없지만 바람직하게는 고압 라디칼 공중합에 의해 얻을 수 있다.The optional copolymerization components described above may be copolymerized in a ratio of generally 15 mol% or less, preferably 10 mol% or less. Such an ethylene-unsaturated carboxylic acid copolymer is not particularly limited, but is preferably obtained by high-pressure radical copolymerization.

(구아니딘 화합물)(guanidine compound)

본 발명에 있어서 구아니딘 화합물이란, 구아니딘 유도체(구아니딘을 포함함) 및 그 염을 의미한다.In the present invention, guanidine compounds mean guanidine derivatives (including guanidine) and salts thereof.

구아니딘 화합물로서는, 예를 들면 구아니딘, 알킬(C1~20)구아니딘(N-메틸 또는 에틸구아니딘, 1,3-디메틸 또는 디에틸구아니딘 등), 방향족 구아니딘(페닐구아니딘, 디페닐구아니딘 등), 비구아니드 화합물(비구아니드, N-메틸비구아니드, N-벤조일비구아니드, N-페닐비구아니드, 시아노비구아니드 등); 구아닐알킬(C1~20)우레탄(구아닐메틸우레탄, 구아닐에틸우레탄 등); 그 밖의 구아니딘 유도체(아미노 구아니딘, 디시아노구아니딘, 구아닐(티오)요소, 시아노구아닐(티오)요소 등) 및 이들의 염산염, 염소산염, 과염소산염, 브롬화 수소산염, 요오드화 수소산염, 황산염, 아황산염, 인산염, 질산염, 탄산염, 및 유기산(포름산, 아세트산, 프로피온산, 술폰산 등)염이 포함된다. 바람직하게는 구아니딘, 알킬(C1~C20)구아니딘, 방향족 구아니딘 및 이들의 탄산염이다. 가장 바람직하게는 탄산 구아니딘이다.Guanidine compounds include, for example, guanidine, alkyl (C1-20) guanidine (N-methyl or ethylguanidine, 1,3-dimethyl or diethylguanidine, etc.), aromatic guanidine (phenylguanidine, diphenylguanidine, etc.), biguanidine, etc. decompounds (biguanide, N-methyl biguanide, N-benzoyl biguanide, N-phenyl biguanide, cyanobiguanide, etc.); Guanylalkyl (C1-20) urethane (guanylmethyl urethane, guanyl ethyl urethane, etc.); Other guanidine derivatives (amino guanidine, dicyanoguanidine, guanyl (thio)urea, cyanoguanyl (thio)urea, etc.) and their hydrochloride, chlorate, perchlorate, hydrobromide, hydroiodide, sulfate, sulfite, These include phosphates, nitrates, carbonates, and salts of organic acids (formic acid, acetic acid, propionic acid, sulfonic acid, etc.). Preferred are guanidine, alkyl (C1-C20) guanidine, aromatic guanidine, and carbonates thereof. Most preferably, it is guanidine carbonate.

(임의 성분)(random component)

본 발명의 성형체용 변성 수지에는, 필요에 따라, 다른 열가소성 수지, 점착 부여 수지, 왁스, 산화방지제, 내후 안정제, 광 안정제, 열 안정제, 자외선 흡수제, 활제, 안료, 염료, 무기 충전제 등 각종 첨가제 등을 배합할 수 있다.The modified resin for molded articles of the present invention may contain various additives such as other thermoplastic resins, tackifying resins, waxes, antioxidants, weathering stabilizers, light stabilizers, heat stabilizers, ultraviolet absorbers, lubricants, pigments, dyes, inorganic fillers, etc., as necessary. can be combined.

[성형체용 변성 수지의 제조 방법][Method for producing modified resin for molded body]

본 발명의 성형체용 변성 수지는, 에틸렌·불포화 카르본산 공중합체와, 구아니딘 탄산염 등의 구아니딘 화합물과, 필요에 따라 임의 성분을 첨가하여 용융 혼련하는 방법에 의해 얻을 수 있다. 용융 온도는 에틸렌·불포화 카르본산 공중합체 및 구아니딘 화합물의 용융 온도 및 분해 온도의 관점에서 바람직하게는 50~300℃, 더 바람직하게는 100~250℃이다.The modified resin for molded articles of the present invention can be obtained by melt-kneading an ethylene-unsaturated carboxylic acid copolymer, a guanidine compound such as guanidine carbonate, and adding optional components as needed. The melting temperature is preferably 50 to 300°C, more preferably 100 to 250°C, from the viewpoint of the melting temperature and decomposition temperature of the ethylene/unsaturated carboxylic acid copolymer and the guanidine compound.

용융 혼련 장치로서는 특별히 제한은 없지만, 예를 들면 배치 혼련기〔예를 들면 반바리 믹서[상품명, Farrel(주)제(製)] 및 니더〕, 연속 혼련기〔예를 들면 FCM[상품명, Farrel(주)제], LCM[상품명, (주)고베제강소제] 및 CIM[상품명, (주)일본제강소제]〕, 단축 압출기, 및 2축 압출기를 들 수 있다.There are no particular restrictions on the melt kneading device, but examples include batch kneaders [e.g. Banbari Mixer [trade name, Farrel Co., Ltd.] and kneader], continuous kneaders [e.g. FCM [trade name, Farrel Co., Ltd.] Co., Ltd.], LCM [brand name, made by Kobe Steel Works Co., Ltd.], and CIM [brand name, made by Nippon Steel Works Co., Ltd.]], a single-screw extruder, and a twin-screw extruder.

본 발명의 성형체용 변성 수지를 함유하는 수지 조성물은, 반발 탄성률, 경도, 및 굽힘 강성률이 우수하기 때문에, 이와 같은 특성이 요구되는 볼이나, 완구 부재, 자동차 부품, 건재(建材) 필름 또는 시트 성형품 등에 유용하며, 특히 골프 볼에 적합하다. 또한, 개질제로서 나일론, PET, PBT 등 다른 수지에 배합해도 된다.The resin composition containing the modified resin for molded articles of the present invention is excellent in rebound elastic modulus, hardness, and bending rigidity, and is therefore used in balls, toy members, automobile parts, building material films, or sheet molded products that require such properties. It is useful for backs and is especially suitable for golf balls. Additionally, as a modifier, it may be mixed with other resins such as nylon, PET, and PBT.

[골프 볼] [Golf ball]

본 발명의 골프 볼은, 본 발명의 성형체용 변성 수지와 필요에 따라 상기 임의 성분을 배합한 재료를 용융 혼련 및 성형하여 얻을 수 있다. 예를 들면, 원피스 볼 재료, 골프 볼의 코어재, 또는 골프 볼의 커버재로서 사용할 수 있다. 커버재에 있어서는, 투피스 볼의 커버재뿐만 아니라, 2중 커버 볼의 외측 커버재로서, 혹은 내측 커버재로서 사용할 수 있다.The golf ball of the present invention can be obtained by melt-kneading and molding a material obtained by mixing the modified resin for molded articles of the present invention and the above optional components as necessary. For example, it can be used as a one-piece ball material, a golf ball core material, or a golf ball cover material. As for the cover material, it can be used not only as a cover material for a two-piece ball, but also as an outer cover material or an inner cover material for a double cover ball.

실시예Example

이하에, 실시예를 들어 본 발명을 더 구체적으로 설명하지만, 본 발명의 범위는 이하에 나타내는 구체예에 한정되는 것은 아니다.Below, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to the specific examples shown below.

[원료][Raw material]

(A) 에틸렌·불포화 카르본산 공중합체(A) Ethylene/unsaturated carboxylic acid copolymer

(a1) 에틸렌·메타크릴산 공중합체(에틸렌:메타크릴산=80:20중량비(에틸렌·불포화 카르본산 공중합체 중의 에틸렌에 유래하는 구성 단위의 함유량이 80질량%이며, 불포화 카르본산에 유래하는 구성 단위의 함유량이 20질량%임), MFR=60(g/10분))(a1) Ethylene/methacrylic acid copolymer (ethylene:methacrylic acid = 80:20 weight ratio (content of structural units derived from ethylene in the ethylene/unsaturated carboxylic acid copolymer is 80% by mass, and The content of the structural unit is 20% by mass), MFR=60 (g/10 min))

(a2) 에틸렌·아크릴산 공중합체(에틸렌:아크릴산=82:18중량비(에틸렌·불포화 카르본산 공중합체 중의 에틸렌에 유래하는 구성 단위의 함유량이 82질량%이며, 불포화 카르본산에 유래하는 구성 단위의 함유량이 18질량%임), MFR=60(g/10분))(a2) Ethylene/acrylic acid copolymer (ethylene:acrylic acid = 82:18 weight ratio (content of structural units derived from ethylene in the ethylene/unsaturated carboxylic acid copolymer is 82% by mass, content of structural units derived from unsaturated carboxylic acid) (18% by mass), MFR=60 (g/10 min))

(B) 탄산 구아니딘(도쿄화성공업주식회사제)(B) Guanidine carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[물성 측정 방법][Method of measuring physical properties]

반발 탄성률, 경도 및 굽힘 강성률은, 아래와 같이 하여 측정했다.The rebound modulus, hardness, and bending rigidity were measured as follows.

(반발 탄성률)(rebound modulus)

성형체용 변성 수지를 160℃로 설정한 열 프레스기를 이용하여 150㎜×150㎜×3㎜ 두께의 시트를 제작했다. 원형으로 타발(打拔)한 시트를 6매 겹쳐 다시 140℃로 설정한 열 프레스기로 층 두께 약 13㎜의 시험편을 제작했다(시험편의 직경 29±0.5㎜). 이 시험편을 23℃, 상대 습도 50%의 분위기에 2주간 보존했다. 그 후, 이 시험편을 류프케(LUPKE) 반발 탄성 시험기로 측정했다. 측정 조건은 JIS K6255:2013에 준거했다.A sheet with a thickness of 150 mm x 150 mm x 3 mm was produced using a heat press machine set to 160°C using modified resin for molded articles. Six circularly punched sheets were overlapped and a test piece with a layer thickness of approximately 13 mm was produced using a heat press set to 140°C (diameter of the test piece was 29 ± 0.5 mm). This test piece was stored in an atmosphere of 23°C and 50% relative humidity for two weeks. Thereafter, this test piece was measured with a LUPKE rebound elasticity tester. Measurement conditions were based on JIS K6255:2013.

(쇼어 D 경도)(Shore D hardness)

성형체용 변성 수지를 160℃로 설정한 열 프레스기를 이용하여 150㎜×150㎜×3㎜ 두께의 시트를 제작했다. 제작한 시트를 폭 20㎜×길이 100㎜의 단책상(短冊狀)으로 타발한 시험편을 23℃, 상대 습도 50%의 분위기에 2주간 보존했다. 그 후, 시트 2매를 겹쳐 Asker 자동 고무 경도계 P1-D형으로 경도(쇼어 D)를 측정했다. 측정 조건은 JIS K7215:1986에 준거했다.A sheet with a thickness of 150 mm x 150 mm x 3 mm was produced using a heat press machine set to 160°C using modified resin for molded articles. The test pieces were punched out of the produced sheets into strips of 20 mm in width and 100 mm in length, and stored in an atmosphere of 23°C and 50% relative humidity for 2 weeks. After that, two sheets were overlapped and the hardness (Shore D) was measured with an Asker automatic rubber durometer type P1-D. Measurement conditions were based on JIS K7215:1986.

(굽힘 강성률)(Bending stiffness rate)

얻어진 성형체용 변성 수지를 160℃로 설정한 열 프레스기를 이용하여 150㎜×150㎜×3㎜ 두께의 시트를 제작했다. 제작한 시트를 폭 20㎜×길이 100㎜의 단책상으로 타발하여, 시험편을 제작했다. 이 시험편을 23℃, 상대 습도 50%의 분위기에 2주간 보존했다. 그 후, 이 시험편을 이용하여 굽힘 강성률을 측정하고, 측정 조건은 JIS K7106:1995에 준거했다.A sheet with a thickness of 150 mm x 150 mm x 3 mm was produced from the obtained modified resin for molded articles using a heat press machine set at 160°C. The produced sheet was punched into a strip of 20 mm in width x 100 mm in length to produce a test piece. This test piece was stored in an atmosphere of 23°C and 50% relative humidity for two weeks. Afterwards, the bending rigidity was measured using this test piece, and the measurement conditions were based on JIS K7106:1995.

<에틸렌·메타크릴산 공중합체를 변성한 성형체용 변성 수지><Modified resin for molded products modified from ethylene-methacrylic acid copolymer>

우선, 에틸렌·메타크릴산 공중합체를 변성한 실시예에 대하여 설명한다.First, an example in which an ethylene-methacrylic acid copolymer was modified will be described.

[실시예 1-1][Example 1-1]

에틸렌·메타크릴산 공중합체 (a1) 76.0g과, 탄산 구아니딘 1.33g(1.7질량%)을 라보플라스토밀(LABO PLASTOMILL)(상품명 「라보플라스토밀 10C-100」, (주)도요정기제작소제)에 넣어, 220℃~230℃, 50rpm으로, 6~12분간 혼련하여 탄산 구아니딘으로 변성한 에틸렌·메타크릴산 공중합체(성형체용 변성 수지)를 얻었다. 에틸렌·메타크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.083이었다.76.0 g of ethylene-methacrylic acid copolymer (a1) and 1.33 g (1.7% by mass) of guanidine carbonate were mixed with LABO PLASTOMILL (brand name “Laboplastomyl 10C-100”, Doyo Jeonggi Manufacturing Co., Ltd.). ) and kneaded at 220°C to 230°C and 50 rpm for 6 to 12 minutes to obtain an ethylene-methacrylic acid copolymer (modified resin for molded articles) modified with guanidine carbonate. The molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups in the ethylene-methacrylic acid copolymer was 0.083.

[실시예 1-2][Example 1-2]

성형체용 변성 수지 중의 탄산 구아니딘의 배합량을 2.65g(3.4질량%)으로 한 것 이외는 실시예 1-1과 마찬가지로 하여 성형체용 변성 수지를 얻었다. 에틸렌·메타크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.17이었다.A modified resin for a molded article was obtained in the same manner as in Example 1-1, except that the amount of guanidine carbonate in the modified resin for a molded article was changed to 2.65 g (3.4% by mass). The molar ratio of guanidinium ions in the modified resin for molded articles to the total number of moles of carboxyl groups in the ethylene-methacrylic acid copolymer was 0.17.

[실시예 1-3][Example 1-3]

성형체용 변성 수지 중의 탄산 구아니딘의 배합량을 3.98g(5.0질량%)으로 한 것 이외는 실시예 1-1과 마찬가지로 하여 성형체용 변성 수지를 얻었다.A modified resin for a molded article was obtained in the same manner as in Example 1-1, except that the amount of guanidine carbonate in the modified resin for a molded article was changed to 3.98 g (5.0% by mass).

에틸렌·메타크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.25였다.The molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups in the ethylene-methacrylic acid copolymer was 0.25.

[실시예 1-4][Example 1-4]

성형체용 변성 수지 중의 염산 구아니딘의 배합량을 5.30g(6.5질량%)으로 한 것 이외는 실시예 1-1과 마찬가지로 하여 성형체용 변성 수지를 얻었다.A modified resin for a molded article was obtained in the same manner as in Example 1-1, except that the amount of guanidine hydrochloride in the modified resin for a molded article was changed to 5.30 g (6.5% by mass).

에틸렌·메타크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.33이었다.The molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups in the ethylene-methacrylic acid copolymer was 0.33.

[실시예 1-5][Example 1-5]

성형체용 변성 수지 중의 염산 구아니딘의 배합량을 7.97g(9.5질량%)으로 한 것 이외는 실시예 1-1과 마찬가지로 하여 성형체용 변성 수지를 얻었다.A modified resin for a molded article was obtained in the same manner as in Example 1-1, except that the amount of guanidine hydrochloride in the modified resin for a molded article was changed to 7.97 g (9.5% by mass).

에틸렌·메타크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.50이었다.The molar ratio of guanidinium ions in the modified resin for molded articles to the total number of moles of carboxyl groups in the ethylene-methacrylic acid copolymer was 0.50.

[비교예 1-1][Comparative Example 1-1]

에틸렌·메타크릴산 공중합체 (a1)을 탄산 구아니딘 (B)로 변성하지 않았다.Ethylene-methacrylic acid copolymer (a1) was not modified with guanidine carbonate (B).

상기 실시예 1-1~실시예 1-5, 및 비교예 1-1에 대하여 측정한 물성을 표 1에 나타낸다. 표 1 중의 「구아니디늄/산기」는, 에틸렌·메타크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비를 나타낸다.The physical properties measured for Examples 1-1 to 1-5 and Comparative Example 1-1 are shown in Table 1. “Guanidinium/acid group” in Table 1 represents the molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups of the ethylene-methacrylic acid copolymer.

Figure 112020097454768-pct00001
Figure 112020097454768-pct00001

표 1에 나타내는 바와 같이, 에틸렌·메타크릴산 공중합체를 탄산 구아니딘으로 변성한 실시예 1-1~실시예 1-5는, 변성하고 있지 않은 공중합체의 비교예 1-1에 비해 반발 탄성률, 쇼어 D 경도 및 굽힘 강성률 모두 높은 값이 얻어졌다.As shown in Table 1, Examples 1-1 to 1-5, in which the ethylene-methacrylic acid copolymer was modified with guanidine carbonate, had a rebound modulus of elasticity compared to Comparative Example 1-1 of the unmodified copolymer, High values for both Shore D hardness and bending stiffness were obtained.

<에틸렌·아크릴산 공중합체를 변성한 성형체용 변성 수지><Modified resin for molded products modified from ethylene-acrylic acid copolymer>

이어서, 에틸렌·아크릴산 공중합체를 변성한 실시예에 대하여 설명한다.Next, an example in which the ethylene-acrylic acid copolymer was modified will be described.

[실시예 2-1][Example 2-1]

에틸렌·아크릴산 공중합체 (a2) 74.0g과, 탄산 구아니딘 1.39g(1.8질량%)을 라보플라스토밀(상품명 「라보플라스토밀 10C-100」, (주)도요정기제작소제)에 넣어, 220℃~230℃, 50rpm으로, 6~12분간 혼련하여 탄산 구아니딘으로 변성한 에틸렌·아크릴산 공중합체(성형체용 변성 수지)를 얻었다.74.0 g of ethylene-acrylic acid copolymer (a2) and 1.39 g (1.8% by mass) of guanidine carbonate were added to Laboplastomyl (brand name “Laboplastomil 10C-100”, manufactured by Toyo Seiki Seisakusho Co., Ltd.), 220 The mixture was kneaded at ℃ to 230℃ and 50 rpm for 6 to 12 minutes to obtain an ethylene-acrylic acid copolymer modified with guanidine carbonate (modified resin for molded products).

에틸렌·아크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.083이었다.The molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups in the ethylene-acrylic acid copolymer was 0.083.

[실시예 2-2][Example 2-2]

성형체용 변성 수지 중의 탄산 구아니딘의 배합량을 4.17g(5.3질량%)으로 한 것 이외는 실시예 2-1과 마찬가지로 하여 성형체용 변성 수지를 얻었다.A modified resin for a molded article was obtained in the same manner as in Example 2-1, except that the amount of guanidine carbonate in the modified resin for a molded article was changed to 4.17 g (5.3% by mass).

에틸렌·아크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.25였다.The molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups in the ethylene-acrylic acid copolymer was 0.25.

[실시예 2-3][Example 2-3]

성형체용 변성 수지 중의 탄산 구아니딘의 배합량을 8.34g(10.7질량%)으로 한 것 이외는 실시예 2-1과 마찬가지로 하여 성형체용 변성 수지를 얻었다.A modified resin for a molded article was obtained in the same manner as in Example 2-1, except that the amount of guanidine carbonate in the modified resin for a molded article was changed to 8.34 g (10.7% by mass).

에틸렌·아크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비는 0.50이었다.The molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups in the ethylene-acrylic acid copolymer was 0.50.

[비교예 2-1][Comparative Example 2-1]

에틸렌·아크릴산 공중합체 (a2)를 탄산 구아니딘으로 변성하지 않았다.Ethylene/acrylic acid copolymer (a2) was not modified with guanidine carbonate.

상기 실시예 2-1~실시예 2-3, 및 비교예 2-1에 대하여 측정한 물성을 표 2에 나타낸다. 표 2 중의 「구아니디늄/산기」는, 에틸렌·메타크릴산 공중합체의 카르복실기의 총 몰수에 대한 성형체용 변성 수지 중의 구아니디늄 이온의 몰비를 나타낸다.The physical properties measured for Examples 2-1 to 2-3 and Comparative Example 2-1 are shown in Table 2. “Guanidinium/acid group” in Table 2 represents the molar ratio of guanidinium ions in the modified resin for molded products to the total number of moles of carboxyl groups of the ethylene-methacrylic acid copolymer.

Figure 112020097454768-pct00002
Figure 112020097454768-pct00002

표 2에 나타내는 바와 같이, 에틸렌·아크릴산 공중합체를 탄산 구아니딘으로 변성한 실시예 2-1~실시예 2-3은, 탄산 구아니딘으로 변성하고 있지 않은 공중합체의 비교예 2-1에 비해, 반발 탄성률, 쇼어 D 경도 및 굽힘 강성률 모두 높은 값이 얻어졌다.As shown in Table 2, Examples 2-1 to 2-3, in which the ethylene-acrylic acid copolymer was modified with guanidine carbonate, showed resistance compared to Comparative Example 2-1, which was a copolymer that was not modified with guanidine carbonate. High values for elastic modulus, Shore D hardness, and bending stiffness were all obtained.

상기한 바와 같이, 본 발명의 에틸렌·불포화 카르본산 공중합체를 탄산 구아니딘으로 변성한 수지는, 반발 탄성률, 경도 및 굽힘 강성률이 우수한 것이다.As described above, the resin obtained by modifying the ethylene/unsaturated carboxylic acid copolymer of the present invention with guanidine carbonate is excellent in rebound modulus, hardness, and bending rigidity.

이 출원은, 2018년 2월 15일에 출원된 일본 특허출원 특원2018-025242호를 기초로 하는 우선권을 주장하고, 그 개시의 전부를 여기에 포함시킨다.This application claims priority based on Japanese Patent Application No. 2018-025242 filed on February 15, 2018, the entire disclosure of which is incorporated herein.

Claims (7)

에틸렌·불포화 카르본산 공중합체를 구아니딘, 알킬(C1~20)구아니딘, 방향족 구아니딘 및 이들의 탄산염으로부터 선택되는 적어도 1종의 구아니딘 화합물로 변성한 성형체용 변성 수지로서,
상기 에틸렌·불포화 카르본산 공중합체의 온도 190℃, 재하 하중 2160g에서, JIS K7210(1999)에 따라 측정한 멜트 플로우 레이트가 20(g/10분) 이상 600(g/10분) 이하인 성형체용 변성 수지.A modified resin for molded products obtained by modifying an ethylene-unsaturated carboxylic acid copolymer with at least one guanidine compound selected from guanidine, alkyl (C1-20) guanidine, aromatic guanidine, and carbonates thereof,
Modification of the ethylene-unsaturated carboxylic acid copolymer for molded articles having a melt flow rate of 20 (g/10 min) to 600 (g/10 min) measured in accordance with JIS K7210 (1999) at a temperature of 190°C and a load of 2160 g. profit. 제 1 항에 있어서,
상기 에틸렌·불포화 카르본산 공중합체가, 에틸렌·(메타)아크릴산 공중합체인 성형체용 변성 수지.According to claim 1,
A modified resin for molded articles, wherein the ethylene/unsaturated carboxylic acid copolymer is an ethylene/(meth)acrylic acid copolymer. 제 1 항에 있어서,
상기 에틸렌·불포화 카르본산 공중합체 중의 불포화 카르본산에 유래하는 구성 단위의 함유량이, 에틸렌·불포화 카르본산 공중합체의 구성 단위의 합계에 대하여, 10질량% 이상 30질량% 이하인 성형체용 변성 수지.According to claim 1,
A modified resin for molded products wherein the content of structural units derived from unsaturated carboxylic acid in the ethylene/unsaturated carboxylic acid copolymer is 10% by mass or more and 30% by mass or less relative to the total of the structural units of the ethylene/unsaturated carboxylic acid copolymer. 제 1 항에 있어서,
상기 성형체용 변성 수지 중의 상기 에틸렌·불포화 카르본산 공중합체에 포함되는 카르복실기의 총 몰수 (A)에 대한 상기 구아니딘 화합물의 구아니디노기 또는 구아니디늄 이온의 총 몰수 (B)의 비(B/A)가 0.05 이상 0.8 이하인 성형체용 변성 수지.According to claim 1,
The ratio (B/ A modified resin for molded articles where A) is 0.05 or more and 0.8 or less. 제 1 항에 있어서,
상기 구아니딘 화합물이 구아니딘 탄산염인 성형체용 변성 수지.According to claim 1,
A modified resin for molded articles wherein the guanidine compound is guanidine carbonate. 제 1 항에 있어서,
상기 성형체용 변성 수지가, 에틸렌·불포화 카르본산 공중합체와, 상기 구아니딘, 알킬(C1~20)구아니딘, 방향족 구아니딘 및 이들의 탄산염으로부터 선택되는 적어도 1종의 구아니딘 화합물을 용융 혼련하여 얻어진 성형체용 변성 수지.According to claim 1,
The modified resin for molded products is obtained by melt-kneading the ethylene-unsaturated carboxylic acid copolymer and at least one guanidine compound selected from guanidine, alkyl (C1-20) guanidine, aromatic guanidine, and carbonates thereof. profit. 제 1 항 내지 제 6 항 중 어느 한 항에 기재된 성형체용 변성 수지를 포함하는 골프 볼.A golf ball comprising the modified resin for molded articles according to any one of claims 1 to 6.
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